Aminoethanesulfonic acid aryl esters



United States Patent 3,190,907 AGETHANESULFGNIC ACID ARYL ESTERS Harry Distler, Gerhard Leihner, Klaus iuergen- Fast, and Ernst-Heinrich Pomrner, Ludwigshafen (Rhine), and Herbert Stummeyer, Mannheim, Germany, assignors to Badische Anilindz Soda-Fabrik Aktiengeseiischaft, Ludwigshaten (Rhine), Germany No Drawing. Filed May 14, 1962, Ser. No. 194,708 Claims priority, application Gil-many, May 20, 1961,

62,57 3 Claims. (Cl. 260-456) This invention relates to new fungicidal compounds.

Especially it relates to aminoethyl sulfonic esters which have fungicidal properties.

We have found that compounds of the formula R1 CH1CH;SO5-O-R R2 in which R may be identical with or different from R and each of R and R denotes an unsubstituted or substituted alkyl or cycloalkyl group or hydrogen or R and R together with the N denote a heterocyclic radical, and R is an unsubstituted or substituted aryl radical or a tetrahydronaphthyl radical, and their salts, are good fungicides.

We have also found good fungicidal properties in the compounds of the formula Ra-N wherein R represents a methyl or cyclohexyl radical, and their salts.

By salts we'mean salts with inorganic or organic acids, for example hydrochloric acid, sulfuric acid, acetic acid or formic acid.

These new compounds are obtained in a simple way by adding on ammonia or amines to a,/3-unsaturated sulfonic acid esters, in accordance with the following reaction scheme:

ice

Patented June 22, 1965 vinylsulfonic acid esters, pentachlorophenylvinylsulfonic acid esters, ocor ,B-naphthylvinylsulfonic acid esters, 2,4,6-

tribromophenylvinylsulfonic acid esters, pyrocatecholdivinylsulfohic acid esters, hydroquinonedivinylsulfonic acid esters and resorcinoldivinylsulfonic acid esters are suitable as initial materials for the production of the compounds to be used according to this invention.

Ammonia or primary or secondary amines are suitable for adding on to these a,,8-unsaturated sulfonic acid esters. Examples are methylamine, dimethylamine, methylethylamine, diethylamine, ethylamine, n-propylamine, isopropylamine, butylamine, dibutylamine, ethylenimine, hexamethylenimine, hexylarnine, decylamine, benzylamine, laurylamine, cetylamine, stearylamine, methylstearylamine, methyllaurylamine, cyclohexylamine, N- methylcyclohexylamine, allylamine, diallylamine, pyrrolidine, N-methylaniline, aniline, or poly-basic aliphatic amines, for example propylene diamine, hexamethylenediamine, ethylenediamine or hydrazine or its substitution products, similarly oxyethylated amines, for example ethanolamine or diethanolamine and also propanolamine or dipropanolamine.

Reaction between the 0:,[3-1111Sfltl1l'fil6d sulfonic acid ester and the amine proceeds even at low temperature or room temperature. In some cases it is necessary to heat the reaction mixture on a waterbath to complete the reaction. The components are preferably used in stoichiometric ratio. An excess of one or other component is usually not necessary because the reaction almost always proceeds quantitatively.

For example the process may be carried out by placing the 0:,fi-11I1Sfltlll'3t6d sulfonic acid ester in the cold in a suitable vessel and allowing the amine to drip in. If onl one hydrogen atom is to be reacted in the case of primary amines, it is necessary to work with an excess of amine and at the lowest possible temperature and to add the sulfonic acid ester to the amine slowly.

Working up the reaction mixture may take place in the conventional ways. For example the reaction product may be poured into water, washed and dried with the usual siccatives. The last traces of solvent or water may then be removed in vacuo at moderately elevated temperature, for example at about 40 to C. Distillation ofthe compounds is not advisable because for the most part they cannot be distilled without decomposition.

The new sulfonic acid esters substituted on nitrogen may be converted into their water-soluble salts with acids. Taurines are formed by saponification of the esters with alkalies.

- The following examples illustrate methods of preparation but do not limit the invention. Unless otherwise stated, parts are by weight. Parts by weight and parts by volume are in the same relation as the gram and milliliter.

EXAMPLE 1 e 618 parts of 40% aqueous dimethylamine solution is dripped during the course of three hours while stirring into 920 parts of vinylsulfonic acid phenyl ester and "236 partsof methanol at 20 C. Then theaqueous layer C. (with partial decomposition).

Analysis.Fo11nd: C, 52.6%; H, 6.4%; O, 20.7%; N,

6.2%; S, 14.0%. Calculated: C, 52.38%; H, 6.59%;

O, 20.94%; N, 6.11%; S, 13.98%.

The following sulfonic acid esters may be obtained in an analogous way:

Example N-CHr-CHz-SOz-O R 7113 HO-CHzCH2 9 -Cl (m.p.-112 to 113 C.)

11 -Cl n1 =1.5335

12 FQCI nD =1.5545

I 13.- nn =L5340 I OH; 14 l(lHa 1.5187

17 -@ooo01115 1.5284

HO-CHg-CH:

Example N--GHC Hz-S o2-o R 7113 HO-CH2CH2 Example /NO H2- 0 H -S O r-O R nD Cl 22 :c1 (m.p. 72 0.

23 01 (m.p.1 34t0138C.)

24 c000n1t 1.5157

Analysis, percent 25 -CH3 N calcu- N found lated C2115 2e /NCHz-CHr-SO:O 5.45 5.3

04H!) 27 /N'CH2CHaSO20 4. 47 4. 7

0H2c11iso2o 2s CH:|I 3.5 3.2

om-cm-som-Q /CH2 CHT-SO20- 29 @N\ 3.0 2.8

0H 0Hso2o- The compounds according to this invention are characterized by very good fungicidal properties. They may be used in admixture with other active substances, as for example acaricides, insecticides, ovicides, herbicides, fungicides and bacterieides.

The fungicides according to the invention may be prepared by mixing the active substances with the conventional diluents or carriers, as for example water, organic liquids, dispersing agents or wetting agents, solid inert substances or mixtures of the said substances. They are used by conventional methods, for example to control fungi on agricultural crop plants.

The following table gives the inhibition values of some of the compounds according to this invention in respect of the fungus Aspergillus niger. Nutrient solutions are inoculated with fungus spores and incubated for hours at 36 C. The extent of the fungoid growth is then estimated according to the following graduated scale:

(1) No fungus growth (2) Slight growth of fungus (3) Moderate growth of fungus (4) Marked growth of fungus (5) Continuous covering of fungus In/ubztzon values wzth respect to Aspergillus nlger Amount of active substance in parts Active substance of per thousand parts of nutrient solution Example No.

What we claim is:

1. A compound selected from the class consisting of the formulae om-cm-sm-o-Q and their acid addition salts wherein:

'R represents a radical selected fromthe group consisting of phenyl, naphthyl, tetrahydronaphthyl, and phenyl containing at least one substituent selected from the group consisting of chloro, methyl, tertiary butyl, octyl, dodecyl and ethoxycarboxyl;

I 3. The compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,241,769 5/41 Dickey et a1 260-456 2,721,875 10/55 Dickert et al. 260-456 2,830,082 4/58 Sexton et a1. 260-456 2,853,416 9/58 Kellog 16733 2,894,971 7/59 ORear et a1 260-456 2,920,997 1/60 Wolf et a1. 167-33 2,978,477 4/ 61 Linden 260456 OTHER REFERENCES Tatsuoka: C.A., vol. 44, p. 4471 (1950). Fujii: C.A., 51, p. 424 (1957). Ringier: Helv. Chim. Acta., vol. 27, pp. 1790-1795 (1944).

CHARLES B. PARKER, Primary Examiner.

'D. T. MCCUTCHEN, NICHOLAS S. RIZZO,

Examiners. 

1. A COMPOUND SELECTED FROM THE CLASS CONSISTING OF THE FORMULAE 